Amine salts of perhalogenated monobasic carboxylic acids

ABSTRACT

A COMPOSITION OF MATTER COMPRISING AN AMINE SALT OF AN UNSUBSTITUTED ALIPHATIC MONOAMINE AND A PERHALOGENATED MONOBASIC CARBOXYLIC ACID. THE ACID IS ONE HAVING THE GENERAL FORMULA: C1(CF2CFC1)NCF2COOH, HERE N IS AN INTEGER FROM 1 TO 4, OR ONE HAVING THE GENERAL FORMULA: F(CF2)MCOOH, WHERE M IS AN INTEGER FROM 3 TO 9. THE SALT IS SOLUBLE IN LUBRICATING OIL AND FUEL COMPOSITIONS, AND SERVES TO REDUCE WEAR, PARTICULARLY SCUFFING WEAR, DURING NORMAL USE OF THE LUBRICANT OR FUEL.

United States Patent Oflice 3,565,926 Patented Feb. 23, 1971 3,565,926AMINE SALTS OF PERHALOGENATED MONO- BASI'C CARBOXYLIC ACIDS Michael J.Furey, Latham, N.Y., assignor to Esso Research and Engineering Company,a corporation of Delaware No Drawing. Continuation-impart of applicationSer. No. 305,805, Aug. 30, 1963, which is a continuation-in-part ofabandoned application Ser. No. 853,471, Nov. 17, 1959. This applicationMay 4, 1966, Ser. No. 547,416

Int. Cl. C09f 7/00 US. Cl. 260-404 7 Claims ABSTRACT OF THE DISCLOSURE Acomposition of matter comprising an amine salt of an unsubstitutedaliphatic monoamine and a perhalogenated monobasic carboxylic acid. Theacid is one having the general formula: Cl(CF CFCl) CF COOH, where n isan integer from 1 to 4, or one having the general formula: -F(CF COOH,where m is an integer from 3 to 9. The salt is soluble in lubricatingoil and fuel compositions, and serves to reduce wear, particularlyscuffing wear, during normal use of the lubricant or fuel.

This application is' a continuation-in-part of application Ser. No.305,805, filed Aug. 30, 1963 now US. Pat. 3,269,- 948, which in turn wasa continuation-impart of application Ser. No. 853,471, filed Nov. 17,1959, said latter application having subsequently been abandoned.

DESCRIPTION OF THE INVENTION This invention relates to salts ofaliphatic amines and monobasic perhalogenated carboxylic acids. Moreparticularly, the invention relates to amine salts formed by reactingprimary, secondary, or tertiary C to C aliphatic monoamines withmonobasic halogen-containing carboxylic acids known as perhalogenatedacids, wherein the number of halogen atoms exceeds the number of carbonatoms. Said salts are useful in lubricating oil and fuel compositions toreduce wear (particularly scufling) during normal use of the lubricantor fuel.

It is well known in the prior art that halogen-containing organiccompounds may be used as additives in mineral lubricating oils toimprove such properties as load carrying ability. However, many of suchhalogenated compounds have been found to be corrosive toward metals. Ithas now been found that by reacting perhalogenated monobasic carboxylicacids with unsubstituted aliphatic monoamines, compounds are formedwhich are not only non-corrosive but which have particular utility asadditives for lubricants and fuels and related liquid compositions inthat they reduce wear and metal-to-metal contact. The perhalogenatedmonobasic carboxylic acids used in this invention have the followinggeneral formulae:

Cl (CF CFCl) DCF2COOH (l) F(CF COOH (2) and The amines useful in formingthe salts of this invention include primary, secondary or tertiary C toC unsubstituted aliphatic and cycloaliphatic monoamines. Specificexamples of amines which may be used include the Primenes (C to C madeby Rohm and Haas, the Armeens made by Armour, (e.g., technicaldodecylamine and technical octadecylamine), propylamine, amylamine,diamylamine, triamylamine, hexylamine, octylamine, oleylamine,linoleylamine and cyclohexylamine. The higher molecular weight amines inthe range of C to C are particularly useful since their salts are moreoil-soluble than those of the lower molecular weight aliphatic amines.The tertiary alkyl amines are also preferred because the higher degreeof branching within the aliphatic chain imparts greater solubility tothe salts formed therefrom.

The liquid compositions to which the salts of this invention may beadded include mineral lubricating oils, synthetic lubricating oils anddistillate fuels boiling in the range from about 50 F. to 750 F. Thelubricating oil may be a mineral lubricating oil, a synthetichydrocarbon oil or other synthetic lubricating oil such as diethylhexylsebacate, carbonate esters, glycol esters such as C 0x0 acid diesters oftetraethylene glycol, other diesters, silicone polymers, complex estersas for example the complex ester formed by the reaction of 1 mole ofsebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid, etc. The lubricating oil will have a viscosity at 210 F.in the range of 30 to 200 SSU, preferably 35 to 100 SSU at 210 F.

Because of the excellent lubricating qualities of the salts of thisinvention they may also be used in hydrocarbon compositions designed forextremely low temperature lubrication. For instance, the aerospaceindustry has developed a need for fluids which may be used attemperatures to 250 F. for a variety of purposes. Hydraulic, heattransfer, shock-absorber and power transmission fluids will be requiredfor use in vehicles traveling on the surface of the moon, for example,where the temperature ranges from 250 F. at midnight to +250 F. atmidday. Isoparaflinic hydrocarbons such as isopentane, isohexane and thelike, are, in general, suitable base stocks for this use. They have awide liquid range, and good stability, but they are not good lubricantsby themselves. Additives are required, and solubility at temperaturesbelow 65 F. limits the choice. However, the Primene salts of thefiuoro-acids of this invention are soluble and are unique in theirsolubilities at temperatures below -100 F. These salts will remaindissolved in isopentane down to the freezing point of -255 F. at 0.25%by weight. Their lubricant qualities are such that the wear of hydraulicpumps, etc. will be effectively controlled.

Other isoparaffinic solvents that may be used to prepare lubricants ofthis general type comprise highly refined synthetic hydrocarbonsobtained, for example, from alkylation and fractionation processes, e.g.from an alkylation reaction involving isobutane and a C to C olefin, orby hydrogenation of branched chain olefins. Such isoparaffinic solventscontain preferably at least volume percent, and more preferably atvolume percent of isoparaffinic hydrocarbons.

Representative isoparaffins include tetramethyl hexanes, tetramethylheptanes and tetramethyl octanes, such as 2,2,4,4-tetramethyl hexane,2,3,3,5-tetramethyl heptane and 2,2,4,6-tetramethyl octane. Thepreferred isoparaflinic hydrocarbon compositions are those wherein thecontents of unsaturated hydrocarbons, such as aromatics and olefins areless than about 1%, and more preferably less than 0.1% by weight and thecontents of cycle and normal parafiins are less than 10%, and preferablyless than about 5% by weight, and those wherein the total concentrationsof non-hydrocarbon impurities such as peroxides, acids, carbonyls,alcohols or other oxygenated compounds are below about 0.01% by weight.

The distillate fuels utilizing the salts of the instant inventioninclude aviation turbo-jet fuels, rocket fuel (MIL-R-25576B), gasolines,kerosenes, diesel fuels and heating oils. Aviation turbo-jet fuels inwhich the amine salts of the present invention may be used normally boilbetween about 50 F. and about 550 F. and are used in both military andcivilian aircraft. Such fuels are more fully defined by US. MilitarySpecifications MILF 5624F, MIL-F-25656A, MIL-F-25554A, MIL-F- 25558B,and amendments thereto, and in ASTM D- 1655-62T. Kerosenes and heatingoils will normally have boiling ranges between about 300 and about 750F. and are more fully described in ASTM Specification D-396 4ST andsupplements thereto, where they are referred to as No. 1 and No. 2 fueloils. Diesel fuels in which the amine salts may be employed aredescribed in detail in ASTM Specification D-975-35T and later versionsof the same specification; Gasolines which may be benefited include bothmotor gasolines and aviation gasolines such as those defined by ASTMSpecifications D-910-56 and D-439-56T.

The liquid lubricating oil compositions utilizing the products of thisinvention will comprise a major proportion of the lubricating oil and0.01 to weight percent, or more, usually 0.1 to 3 weight percent, basedupon the total weight of the composition, of the amine salts of thehalogen-containing acids. The liquid fuel compositions will likewisecomprise a major proportion of the liquid fuel and about 0.001 to 5weight percent, based on the total weight of the composition, of theamine salts of the halogen-containing acids, and more usually 0.01 to0.20 weight percent.

Other additives which may be used in the liquid compositions includeviscosity index improvers, pour point depressants, corrosion inhibitors,thickeners, sludge dispersants, rust inhibitors, anti-emulsifyingagents, antioxidants, dyes, dye stabilizers and the like.

The amine salts of this invention are prepared by simple addition of thehalogen-containing monobasic carboxylic acid to about an equal molarproportion of the C to C aliphatic amine. The reaction is exothermic andwill normally proceed at temperatures between 70 and 200 F. Care shouldbe taken to prevent the temperature from exceeding 200 F. since watermay be driven off and an insoluble amide might be formed in place of theamine salt reaction product of this invention.

The following examples which include a preferred embodiment, aresubmitted as illustrating the practice of this invention, but are in noway intended to limit the invention.

EXAMPLE 1 To illustrate the preparation of the amine salts of thisinvention and their use in lubricating oil compositions, an amine saltof Cl(CF CFCl) CF COOH Kel-F acid 8114) was prepared by adding one mole(480 grams) of the acid to one mole of Primene JM-T (315 grams based onneutralization equivalent) at room temperature with constant stirring.Primene JM-T is a mixture of tertiary alkyl primary amines (C18H37NH2 toC H NH The reaction occurred immediately and the temperature rapidlyclimbed to 100 F. The product when cooled to room temperature was aclear amber viscous fluid. The percent chlorine in this product was17.2% which compares well with the theoretical value of 17.8%. This saltwas then added in several concentrations to a mineral lubricating oil ofMid-Continent origin having a viscosity at 210 F. of 40.8 SSU. The saltwas also blended in 1 weight percent concentration in two separate SAEW-30 lubricating oils containing detergent inhibitors. Each of theresultant lubricating oil compositions was then tested for valve trainwear, which is a problem of increasing importance in automotivelubrication. The tests were carried out in a laboratory multicylinderengine equipped witth radioactive steel valve lifters. These tests wererun for three hours at 1000 r.p.m., no load, with normal valve springtension, and the jacket outlet temperature controlled to F. The valvelifter wear is calculated from the total amount of radioactive weardebris contained in the oil recovered from the three-hour test. Theengine is flushed with fresh oil before and after each test run. Underthse conditions, the radioactive Wear test gives good correlation withfield tests using the same oils, engines, and valve train metallurgy.This test is more fully described in the July, 1958 issue of LubricationEngineering, a journal of the American Society of Lubrication Engineers,pages 302 to 309.

The results obtained with each base oil and each blend are given inTable I, which follows.

TABLE I.-INFLUENOE OF PRIMENE .TM-T SALT OF Cl (CFzCFCDs CFzCOOH ONVALVE TRAIN WEAR Relative valve lifter wear 1 10W-30 SAE minerallubricating oil base.

2 Mixture of 37.5% calcium sullonate and 62.5% P28 treated bariumiso-nonyl phenol sulfide. (Additive concentrate containing approximately58 Wt. percent mineral oil.)

3 Mixture of barium iso-nonyl phenol sulfide, P285 treatedpolyisobutylene of 1100 molecular weight and a barium alkyl benzenesullonate. Contains 1.28 wt. percent phosphorus, 8.59 wt. percent bariumand 4.18 Wt. percent sulfur. (Additive concentrate containingapproximately 50 wt. percent mineral oil.)

The data in Table I show that the salt of this invention was eifectivenot only in a simple blend in mineral lubricating oil but was alsoextremely effective in reducing valve train wear when used inlubricating oils which also contained conventional detergent inhibitors.

The Primene salt was also tested in the SOD Bearing Corrosion Test at340 F. This is a test for oxidation stability and corrosion resistanceand involves determination of bearing weight loss and oil viscosityincrease when a copper-lead bearing is immersed in the test oil at 340F. for 20 and 24 hours. Results are shown in Table II.

TABLE II.EFFECT OF PRIMENE JM-T SALT OF XlP(g4IO g%FCD3CFzCOOH ON SODBEARING CORROSION Wt. percent Primene JM-T/Cl (CFzCFCDaCFzCOOH salt inTables I and II illustrate the fact that salts of this invention serveas wear reducing additives without adversely affecting corrosion Whenused in internal combustion engines.

The extreme pressure properties of the primene salt in minerallubricating oils were tested by means of the standard 4-ball EP test.This test uses an apparatus having three lower balls fixed in a potwhich also h0lds the test lubricant. The fourth ball, held in a chuck,is pressed against the three lower balls with a known force and isrotated at a selected speed. The machine is usually 0perated with thelubricant at ambient temperature, with the upper ball rotating at 1800r.p.m. A series of short duration tests are run at gradually increasingload increments until initial seizure occurs. Table III illustrates themaximum load which could be carried in the 4-ball EP test for one minutewithout film failure or scufiing.

TABLE 111 Effect of primene JM-T salt of Cl(CF CFCl) CF COOH on extremepressure properties of oil Wt. percent additive in mineral oil 40.8 SSUviscosity metallic contact occurs in a given period of time. Frictionbetween the ball and cylinder is recorded simultaneously with contact.This is noted as coeflicient of friction, which is the ratio of frictionforce to the load. It has been found that there is, in general, a goodcorrelation at 2l0 F.: 5 between metallic contact measured in thismanner and Maximum load earned 1n 4-ball E.P. Test 1 111 kgthe amount ofsurface damage which occurs.

None 4 The evaluations of the compositions were obtained un- 0.1 0 derthe following conditions: 1.0 70 AISI 52100 steel 10 1 I) b 11 1Steel-on-steel at 1800 r.p.m. /2 dlama on fil hiaaimum loadffithat canbe carried for 1 minute without Syst m; 1%" diam, cylinder m 111111901Speed (r.p.m.) 240 EXAMPLE 2 Running time (min.) 32 This exampleillustrates the reduction in valve train 15 011 temperature 0 77 wearobtained in a Volkswagen engine Where small quan- Load (grams) 1000:4000 tities of an amine salt of this invention are added to theCalculated meal} Hertz lubricating oil. The Volkswagen cyclic test is avalve train Pressure P 88,000; 141,000 Wear and intake valve deposittest. It is designed to The results of the tests are summarized in TableV and evaluate the protection against valve train Wear in the show thatthe addition of only 0.1% by weight of the Volkswagen engine which anoil affords and to evaluate Kel-E ac1d salts of various amines markedlyreduces the tendency of an oil to give deposits on the undersidesmetallic contact. of int k alve TABLE V.METALLIC CONTACT TESTS I t t 11't t- Test operatmg cond1t1ons Addifiyein base mineral men me a cycle:011 (wt. percent) 240 g. 1, 000 g. 4, 000 g. 5 min. at 600 :25 r.p.m. Noload 8125/10? 92.0 97.9 98.2 nmene e ac sa t 42.8 80.6 94.3 10 f at1200:25 -P- N0 load 0.1% ro lamine Kel-i acid salt 0.3 0.7 99.1 1 min.at shutdown 1% amylamiue/Kel-F acid salt.-. 1. 1 2.0 2. 3 3O 0. 1%dramylamine/Kel-F acid salt- 11. 8 24. 8 86. 7 Test duratlon and thetest results are reported in Table y amu1e/Ke1Fac1d salt.-- 10.2 12.462.6 IV 0.1% octylam1ne/Kel-F acid salt 59.5 77.9 80.6

TABLE IV.VOLKSWAGEN VALVE TRAIN WEAR Intake Tappet wear in Cam wear inTotal wear in 0.0001 Tappet valve de- 0.0001 in. 0.0001 in. in. failuresposit wts. Additive, wt. percent in Tlme 0.001 in gms base oil 1 (hrs.)Average Range Average Range Average Range wear) (average) 33. 4 (767)50.1 (17-108) 48 (-54) 98 (68-160) s 0. 93 0.5 (0-1) 1.1 (0-3) pg 1-31.5 (04 3 (1-5) Test stopped at 79 hrs. because of electronic controldifilenlties. Extrapolated.

1 10W-30 SAE mineral oil (commercial lubricant containing 4 vol.percent. of the detergent-inhibitor of Footnote 3 of Table I).

2 Primene JIM-T salt of Cl (CF2CFC3) CFzCOOH.

It is seen from Table IV that the amine salt of the invention was veryeffective in reducing valve train wear.

EXAMPLE 3 In order to demonstrate further the scope of the presentinvention, amine salts of Cl(CF CFCl) CF COOH (KelF 8114) were preparedby adding 1 gram mole (480 grams) of the acid to 1 gram mole of each ofthe following amines: Primene JM-T, propylamine, amylamine, diamylamine,triamylamine and octylamine. The resulting salts were added to separateportions of a mineral lubricating oil of Mid-Continent origin having aviscosity at 210 F. of 40.8 SSU.

The respective oil compositions were tested for wear and scuffing in arotating cylinder apparatus designed to measure metallic contact andfriction between sliding, lubricated surfaces. The test is more fullydescribed in the paper Metallic Contact and Friction Between SlidingSurfaces, by M. J. Furey, ASLE Transactions, vol. 4, pages 1-11, 1961.The paper is by reference herewith incorporated in its entirety in thisapplication. The apparatus consists basically of a fixed metal ballloaded against a rotating steel cylinder. The extent of metallic contactis determined by measuring both the instantaneous and average electricalresistance between the two surfaces. It is expressed as the percent ofthe time that EXAMPLE 4 It has further been found that amine salts ofperfluoro acids having the general formula F(CF COOH, where m may rangefrom 3 to 10, are extremely effective in reducing wear and metalliccontact. In order to demonstrate this, a Primene JMT salt ofdecapentylfluoro octanoic acid was prepared in the following manner andthen subjected to a series of tests.

Separate solutions were made of 0.1 mole (30.3 g.) of Primene JM-T in g.of tetrahydrofuran and 0.1 mole (41.4 g.) of decapentylfiuoro octanoicacid in 200 g. of tetrahydrofuran. The acid solution was slowly added atroom temperature to the amine solution with stirring. The temperaturerose from 25 C. to 35 C. The tetrahydrofuran was then evaporated bypassing nitrogen over the solution overnight followed by heating to 75C. for 5 minutes. The yield was 72.2 grams, indicating that only 0.5gram of tetrahydrofuran remained. The :final product was an amber,viscous fluid, soluble in hydrocarbons. Thereafter, 0.1% by weight ofthe above amine salt was dissolved in a straight mineral oil, namely asolvent-extracted distillate having a viscosity of 35 cs. at 77 F. and aV.I. of 110, and the resulting test sample 7 subjected to theBall-on-Cylinder test of Example 3. The

results obtained appear in Table VI.

TABLE VI.-EFFEOT OF PRIMENE/ CTFIECOOH SALT ON METALLIC CON- TAC'I INBALL ON CYLINDER TESTS Percent metallic contact As shown by Table VI,the Primene-C F COOH salt is extremely effective in reducing metalliccontact over a wide range of loads.

Further evidence of the effect of the above amine salt on wear wasobtained in the Four-Ball Wear Test. The test was conducted as follows:Test solutions were placed in the cup of the machine and heated to 100C. The test cup contained 3 steel balls which were fixed in position bya screw cap. A fourth steel ball, held in a chuck, was pressed againstthe 3 lower balls with a force of 40 kilograms and rotated at 1200r.p.m. for a period of 1 hour. At the end of the test, the amount ofwear was determined by measuring the diameter of the wear scar on eachof the balls and averaging the results. As can be seen from the data inTable VII, the addition of 0.1% by weight of Primene-C F COOH salt tothe base oil reduced wear by over 60%.

TABLE VII Effect of Primene/C F COOH salt on wear in the 4-bal1 weartest 1 Additive in mineral Avg. scar diam. in lubricating oil: 4-balltest mm.) None 1.65 0.1% Primene/C F COOH salt 0.59

-Steel-on-steel, 40 kg. load, 1 hr., 100 0., 1200 1'.p.m.

EXAMPLE 5 The utility of the amine salts of the present invention Wasfurther evaluated by adding Primene salts of decapentylfluoro octanoicacid and Kel-F 8114 acid to various liquid compositions. The resultingtest compositions were tested in Ryder Gear Apparatus (E.A. Ryder, ASTMBulletin 184. 41 (1952)). The results of those tests appear in TableVIII.

TABLE VIII Effect on load-carrying capacity in the Ryder gear test Ryderrating Test composition: (lbs/inch) Synthetic lubricant A (1) 1650A+0.2% Primene-C F COOH salt 2250 Synthetic lubricant B (2) 2500 B|-0.2%Primene-C F COOH salt 2760 B+0.25% Primene-Kel-F (8114) acid salt 3010Jet fuel (3) 400 Jet fuel+0.0l% Primene-Kel-F (8114) acid salt 980 Jetfuel+0 1% Primene-Kel-F (8114) acid salt 2290 1 A blend of 69% of (ii-2ethyl hexyl scbacate with 17.3% C8 azelate and 13.7% C10 adipate. Theoil also contained tricresyl phosphate for load-carrying capacity.

2 A blend of 55% trimethylol-propane triester of pelargonic acid and 45%complex ester of neopentyl glycol, trimethyl pentanol and sebacic acid.

A highly isoparafiinic fuel of 375-500 F. boiling range, liigltitthermal stability, low freezing point and low sulfur con en The abovedata further demonstrate the effectiveness of the amine salts of thepresent invention in improving the antiwear and anti-scufliingproperties of both hydrocarbon liquids and synthetic ester lubricants.

Silicone fluids have certain properties which make them of interest aslubricants. For example, they have uniquely 8 low temperaturecoeflicients of viscosity. However, silicones also have a seriousdrawback: they are very poor lubricants under conditions of boundarylubrication and particularly when the rubbing surfaces are steel. Undersuch conditions, the use of silicones as lubricants leads to highfriction and wear, galling and seizing.

EXAMPLE 6 The benefit of employing the amine salts of the presentinvention in silicone fluid lubricants is shown by the data in Table IX.A blend was prepared bysimple mixing of 1 wt. percent of the PrimeneJM-T salt of decapentafluoro octanoic acid, prepared as described inExample 4, and 99 wt. percent of Dow Corning methyl silicone fluidDC-200. This blend was compared with the methyl silicone fluid alone intests run with the ball-on-cylinder described in Example 3. Coefficientof friction and average wear were measured at various loads as shown inTable TABLE IX.EFFEOT OF PRIMENE .IM-T SALT OF C1F15COOH ON FRICTION ANDWEAR IN SILICONES Additive in methyl silicone fluid 1 Load Coeff. ofAvg. wear 1 DC200-10 (10 cs. vicosity at 77 F.) made by Dow-Corning. 2Ball-on-cy1inder tests with AISI 52100 steel, 240 r.p.m. 32 min. 3Discontinued at 1 min. due to excessive chattering.

It can be seen that the silicone by itself gave extremely high friction.In fact, the vibration was so excessive that the metallic contact datawere of no value. At the highest load (240 g.), the test had to bestopped right away because of the high friction and excessivechattering. On the other hand, the silicone containing the additive ransmoothly at all loads and gave less than one-tenth the friction. Inaddition, wear at the lower loads was cut in half. The extent ofmetallic contact with the additive fluid ranged from 48 to 61% dependingupon the load. This compares very favorably with that observed withBayol 55, a white oil of the same viscosity, which gave from 47 to 86%metallic contact.

It is thus seen that the addition of a minor amount of the Primene JM-Tsalt of C F COOH to dimethyl silicone markedly reduces friction, wearand surface damage in a steel-on-steel system. This is of great interestbecause most of the conventional antiscuff and antiwear additivesdeveloped for use in hydrocarbons are not soluble in silicone fluids,and most of those that do dissolve in silicones do not give the expectedbenefit.

Silicone blends containing the Primene salt are perfectly clear and showno signs of haze or settling even after two months storage.

The amine salts of this invention are also useful for forming antiwearfilms under situations where the carrier liquid may not remain in placeto do the lubricating. One application of this technique is to employthe amine salt as an additive or pretreatment to use in rocket fuel sothat fuel pumps pumping kerosene will not 'wear out in a few minutes.Another application is one in which a complex device cannot becontinuously lubricated but must be lubricated or treated so that thebearings etc. can travel a. fair distance before being lubricated again.An example is a plastic extruder or biaxial stretching machine such asthat described in US. Pat. 3,150,433 of E. Kampf. Such a machinecontains thousands of bearings and other con tacting sliders and must gothrough a high temperature oven for an appreciable distance and lengthof time. Ordinary lubricants and even high temperature greases apparently do not work satisfactorily under such conditions. Here the bestapproach is to use a material capable of forming very durable films,films which will protect the surfaces from wear and which will last forquite a while until replenishing lubricant can reach those surfaces. Ablend consisting of 1 wt. percent of the Primene JMT salt of KelF acid8114, prepared as described in Example 1, in 99 wt. percent of a solventneutral mineral lubricating oil (100 SSU viscosity at 100 F.)successfully lubricated, with no difliculty whatever, the hardenedstainless steel slipper bearings and hardened steel guideways of astretching machine of the type described in U.S. Pat. 3,150,433 which'was being used for stretching a thermoplastic web at 350 F. Incontrast, when these parts were lubricated with a conventionaloxidation-inhibited lubricating oil, undesirable deposits built up onthe slipper bearings and guideways, and galling of the surfaces wasencountered.

There is no intention that the scope of this invention be limited to thespecific embodiments herein described. The invention is defined by theappended claims.

What is claimed is:

1. As a composition of matter, an amine salt of an unsubstituted alkyl,alkenyl, or cyclohexyl monoamine having from about 12 to 24 carbon atomsper molecule and of a halogen-containing acid selected from the groupconsisting of perhalogenated monobasic carboxylic acids have the generalformula:

where n is an integer from 1 to 4, and perhalogenated monobasiccarboxylic acids having the general formula:

where m is an integer from 3 to 9.

2. A composition according to claim 1 wherein said amine is atertiary-alkyl primary amine.

3. A composition according to claim 1 wherein said halogen-containingacid is: Cl(CF CFCl) CF- COOH.

4. A composition according to claim 1 wherein said halogen-containingacid is F(CF COOH.

5. A composition according to claim 1 wherein said amine is a mixture oftertiary C to C alkyl primary amines.

6. A composition according to claim 1 wherein said amine is a mixture oftertiary C to C alkyl primary amines and said halogen-containing acid isdecapentafluoro octanoic acid.

7. A composition according to claim 1 wherein said amine is a mixture oftertiary C to C alkyl primary amines and said halogen-containing acid isReferences Cited UNITED STATES PATENTS 2,353,169 7/1944 Lincoln et a125254.6X 2,567,011 9/1951 Diesslin et al 260465.7 2,812,307 11/1957Sai-ves 25254.6UX 2,875,072 2/1959 Dielman et a1. 106-14 2,877,1823/1959 May 25254.6UX 3,232,970 2/ 1966 Hauptschein et a1. 2604082,824,884 2/1958 Barnhart et a1. 260404 3,269,948 8/1966 Furey260-501.16 3,444,170 5/ 1969 Norman et al. 260404 LEWIS GOTTS, PrimaryExaminer G. HOLLRAH, Assistant Examiner U.S. Cl. X.R.

